Methine dyestuffs



Patented Oct. 10, 1950 UNITED STATES e TENT OFFIC METHINE DYESTUFFS Jules Edmond Beelsmans, Antwerp-Borgerhoutp Belgium, assignor' to Gevaert Photo-Producten N. 'V., Mortsel-Antwerp,Belgium, a company of Belgium No Drawing. Ap lication June 10, 1947, Serial No. 753,818. In Great Britain June 1'7, 1946 3 Claims. (01.260-24013) This invention relates to mam-115655015 methine dyestufis,

It is an object of this inventionto provide a new class of methine or polymethine dyestuffs.

To accom-plish this object and others which will hereinafter appear, my invention resides in the new product which is more particularly described. in the following specification and sought to be defined in the appended claims,

I have found a new class of methine or polymethine dyestufis which contain, at least at one side of the central methinegroup or polymethine chain, a'1,2,i-oxodiazole nucleus and an electronegative group linked to the same C atom, this electronegative group being e. g. cyan,

anion, and a group of the formula --CAR1 wherein A is 0 or S and R1 'is'alkyl, substituted alkyl, alkoxy, carbalkoxy, aryl, substituted aryl, an amino or substituted amino group.

More particularly, I have found a new 'classot methine or polymethine dyestuffs Which may be represented by the following general formula NO Y I R(H3 l(=LL),.-1=Z

wherein R is alkyl, substituted alkyl, aryl or substituted aryl; Y is an electronegative group, such as cyan,

anion, and a group of the formula -CA-R.1 WhereinA is 0 or S and R1 is alkyl, substituted alkyl, alkoXy, carbalkoxy, aryl, substituted aryl, an amino or substituted amino group; n is a positive integer; L is a methine group either substituted or not; Z is any of the following:

wherein X and D are substituents which when linkedflto a methylene group X' CH2'D. activate the same, X may be an electronegative group whereasD representsa heterocyclic nucleus-for example, oxodiazole or benzothiazole, or X may,

7 for example, be-a 'carbonyl grouplinked 1:013 in such a way that X and D form part'of a heterocyclic five or six membered ring, such as a pyrav mg action upon photographic silver halide emulsions. The dyestuffs are prepared from thebases f O Y R-t t-cHiY obtainable accordin to the general methods described in Berichte 18 (1885), 10534086, and 22 (1889), 2412-2459.

These products are reacted, for instance, with compounds of the general formula or their hydrochlorides. V

The reaction may be carried out in such a way that only 1 mol of these compounds reacts with 1 mol of an oxodiazole base to obtain products of the formula i 1' R-C CC=(OH OH) 1=CHNHC(|H5 Since these products react upon reactive methylene groups in general, dyestufis may thereby be prepared, for example, corresponding to the formulae N Y Y' 0-N II J l I l R-c O=(LL),.-1=L-CH-C CR' O N (B) These may be symmetrical or asymmetrical.

dyestuffs. For example, Y may be different or identical with Y, also R and R ma be identical or different or The dyestuffs represented by the Formula C may also be prepared by condensation of hemioxonoles with the oxodiazole bases.

The dyestufis represented by the Formula D, too, may be obtained by condensation with the oxodiazole bases of quaternary cyclammonium salts which have a reactive group such, as for example, a halogen, alkylmercapto, arylamino or acylarylamino group in alpha position or gamma position with respect to the nitrogen atom, optionally at the end of a polymethine chain. They may also be prepared by treating a mixture of an oxodiazole base and a quaternary cyclammonium salt with an orthoester. Thus, a mixture of dyestuffs is obtained which owing to the great difierence in solubility can be separated in a simple way.

Lower aliphatic alcohols, pyridine, the anhydrides of lower fatty acids, for example, acetic acid anhydride, are suitable reaction media for all of these condensations.

Inmost cases acid-binding condensing agents are added, for example, sodium acetate, or also strong bases such as triethylamine or piperidine.

The oxodiazole-polymethine dyestuffs are very stable. They are suitable for sensitizing silver halide emulsions and when mixed with other sensitizers, make possible very favorable effects. By suitable substitution in one or another part of the molecule, their properties or diffusion or solubility can be adapted to predetermined purposes, for example, for use as filter or anti-halation layers.

My new compounds can also be used for dyeing fabrics and other materials.

Some specific examples illustrating my invention are given hereinafter.

Example 1 8.25 g. 3-(p-tolyl)-5-acetonyl-1:2:4:-oxodiazole are melted whilst stirring with 15 g. diphenyl-formamidine at 135 C. on an oil bath.

After cooling and crystallizing from alcohol, fine white crystals are obtained.

4 Melting point 161162 C. Probable structure according to the following formula meg-( l-( J=GHNHCsHs N Analysis:

Calculated: 13.16% N 13.12% N Found. 131.3% }Dumas Example 2 1 g. 3- (p-tolyl) -5-(s-anilido-a-acetyl-vinyl) 1:2:4-oxodiazole and 0.8 g. 2-methyl-benzothiazole-ethyl-bromide in 15 cm. alcohol are boiled for 15 minutes with 0.43 cm. triethylamine.

After cooling, filtering, thereby using a filter pump, and recrystallizing from alcohol, orangered crystals are obtained.

Melting point 200-201 C. Probable structure according to the following formula CzHs The dyestuff has a strong sensitizing action upon silver halide emulsions with a maximum at 520 m and reaching to 550 mp.

The same product can also be formed by reaction of 24i-anilido-vinyl-benzothiazole-ethiodide upon 3- (p-tolyl) -5-acetonyl-1:2:4-oxodiazole.

Analysis.Calculated: 7.94% S. Found: 8.01% S; 7.92% S.

Example 3 1.5 g. 3-(p-carbethoxybenzyl) -5-cyanmethyl- :2:4-oxodiazole are boiled in alcohol with 0.5 cm. triethylamine, 0.5 cm. acetic anhydride and 2.25 g. 2-p-(analidovinyl) -benzothiazoleethiodide for 15 minutes. After cooling, filtering and recrystallizing from alcohol, beautiful yellowish crystals are obtained.

Melting point 196 C. Probable structure according to the following formula This dyestuif sensitizes silver halide emulsions with a maximum at about 510 my.

Example 4 1.44 g. Z-B-anilidovinyl-S-methyl-1:3:4 thiodiazole-benzylbromide with 1 g. 3-(p-tolyD-5-cyanmethyl-l12:4-oxodiazole in 10 cm. alcohol and 0.5 cm. acetic anhydride are boiled for five minutes, while 0.7 cm. triethylamine dissolved in alcohol are added drop by drop. After cooling, filtering, washing with water and alcohol and recrystallizing from alcohol, a product melting at 223.5-224.5 C. is obtained. The probable structure is according to the following formula Ha C- C S ON O-N l pennant 2504....

PCBHE 2,525,015 6 This dyestuif sensitizes a silver chloride emul- Example 8 slon Wlth aimaxlmum at 490 1.09 g. of the product obtained in Example 7 Example 5 Y with 0.66 g. 3-(p-to1yl)-5-cyanmethyl-1:2:4-

ec -50 c. 2.25 g. 2- -an1l1dov1n l-benzoxazole-p-car- PXOdIaZPIe ale heated for 7 hour? a boxy-benzyl-brgmide and 1 .08 g. 3-(p-t0lyl)-5- a P QQ and ,pyndme wllih acetonmd.2:4 oX0diaZo1e in cmg pyridine cm. of piperidme. The reaction product 1s prewith cm} acetic anhydride are heated for one cipitated with water and recrystallized from hour on a boiling water bath; The reaction alcohol product is filtered and six times digested with 10 alcohol, dissolved in a mixture of alcohol and water with an excess of an aqueous sodium bisition. Probable structure according to th following formula carbonate solution, precipitated with hydro- This intense pink dyestuff sensitizes strongly chloric acid whilst mechanically stirring, filtered a silver brOmo-iodide emulsion with a maximum and washed with water and alcohol. The probat 545 mu.

able structure is according to the following formula CH3 6.48 g. 3-(p-tolyl) -5-ac etonyl-1:2:4-oxodia- (3:0 0 N zole are dissolved in 50 cm. anhydrous alcohol I HO at 50 C. 8.52 glutacondialdehyde-dianilhydro- Example 9 I /C:CHCH:CMG\ chloride, 4.2 cm. triethylamine and 15 cm. alco- N hol are added. The mixture is stirred and kept I 01120-00011 for 20 hours at room temperature. After recrystallization, beautiful sheets with metal gloss This dyestuff sensitizes a, silver chloride emult t 1 5 r bt ined, This product sion with a maximum at e80 mu. gives a pink solution in alcohol. The probable Emmple 6 structure is according to the following formula 1.1 g. 3 omethoxy phenyl) 5 acetonyl- 1:2:4-oxodiazole With1.93 g. 2-anilidovinyl-ben- (13113 zothiazole-ethiodide in anhydrous alcohol are fi (3:0 I boiled for 15 minutes with 0.48 cm. acetic anmeO-o c-c: women-omon-nn-ona. hydride and 0.65 cm. triethylamine. After crystallizing from alcohol, a product is obtained WhlCh melts at 195 -196 C. The probable struc- Example 10 ture is according to the following formula (3H3 l0 cm. of an alcoholic solution of 3.24 g. 3-(p- 0:0 OW tolyl)-5-acetonyl-1:2:4-oxodiazole and 2.84 g.

glutacon-dialdehyde-dianil-hyd'rochloride are refluxed for 10 minutes with 1.4 cm. triethyl- H N 00m amine. After recrystallizing from alcohol, an

intense blue dyestuff is obtained. Probable structure accordin to the following formula halide emulsions with a broad maximum at Melting point 156--158 0.

about 510 m h Example 7 Example 11 1 -(pt01y1 -cy nm hy1-1- 0.59 'g. 3 -.(p tolyl) 5-(6- anilido 1'- cyanzole and 1.29 g. ,8-anilido-,acroleinanil-hydrochlo 1;3:5-hexatrieny1)1:2:4-oX0diaz0le and 0.33 ride are kept for 7 hours at room temperature g 3 -(p-tQ1y1)- 5 cyanmethyl- 1:214 oxodiin a ohol W th 1 11101 fi y A Product azole are dissolved in 10 cm. of a mixture of is obtained which melts at l96-;1 98 C. with. deidine' nd 1c h 1 at abo t 50 0. 0,61 0111. co p e p o b e Structure is T of piperidine are added and the solution is kept 0 t e following formula for 4 hours at room temperature and for 1 6N hours; at 40-50"" C. the product is filtered while VII l f' yet warm, and recrystallized from alcohol. An O'K 9 intense blue dyestufi'melting at 178180 is V obtained. The probable structure is according This product forms yellow crystals. to the following formula NO CN ON ON Melting point at 180-190 C. with decompo- This dyestufi sensitizes strongly 'a silver bromo-iodide emulsion between 520 and 720 mp.

3 tolyl 5 (6'anilido 1' cyan 1:3:5- hexatrienyl)-1:2:4-oxodiazole was prepared in the manner described in Example 9; it melts at 184 C.

Example 12 This dyestufi sensitizes a silver halide emulsion with a broad maximum at 610 m This dyestuff is also obtained by reacting 3-(ptolyl) 5 (4 anilido 1' cyan 1' 3' butadienyl) -1 :2 4-oxodiazole with 2-methyl-benzothiazole-ethiodide in acetic anhydride with triethylamine.

Example 13 2.04 g. 2-anilido-vinyl-benzothiazole-ethiodide and 1.6 g. 3-(p-tolyl) 112:4-oxodiazolyl 5-methyl-pyridinium chloride are dissolved in absolute alcohol. 0.7 cm. triethylamine and 0.5 cm. acetic acid anhydride are added. The mixture is boiled for 5 minutes. The precipitated product is filtered, Washed with water and recrystallized from alcohol. Red crystals decomposing at 240 C. are obtained. Probable structure according to the following formula This dyestufi sensitizes a silver chloride emulsion with a maximum at 510 mp.

Example 14 11.6 g. 2-anilido-vinyl-benzothiazole-ethiodide and 7 g. 3-(p-toly1)-1:2:4-oxodiazolyl-5-acetic acid ethylester are dissolved in absolute alcohol. 4 cm. triethylamine and 3 cm. acetic acid anhydride are added. The mixture is boiled for 5 minutes. After cooling the precipitated product is filtered and recrystallized from alcohol. A yellow dyestulf 'melting at 174-176 C. is obtained. Probable structure according to' the following formula It. is believed that my invention, as well as the advantages thereof, will be apparent from the foregoing detailed description. It will also be apparent that while I have shown and described preferred examples of my invention, changes may be made without departing from the spirit of the invention, as sought to be defined in the following claims.

I claim:

1. A dyestufi corresponding to the general formula:

wherein Zrepresents the non-metallic atoms necessary to complete a member selected from the group consisting of five-membered heterocyclic rings and five-membered heterocyclic rings bearing a fused-on arylene group, Y represents a member selected from the group consisting of CN and acetyl, R represents a member selected from the group consisting of aryl and aralkyl, R represents a member selected from the group consisting of alkyl and aralkyl, and n represents a positive integer of from 2-to 3.

2. A dyestuff corresponding to formula J ULES EDMOND BEERSMANS.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENT Number Name Date 2,153,169 Brooker Apr. 4, 1939 2,185,798 Steven Jan. 2, 1940 2,191,810 Stevens Feb. 27, 1940 2,226,156 Brooker Dec. 24, 1940 2,312,068 Bauer Feb. 23, 1943 2,345,094 Brooker Mar. 28, 1944 2,393,745 Brooker Jan. 29, 1946 2,415,927 Anish 'Feb. 18, 1947 

1. A DYESTUFF CORRESPONDING TO THE GENERAL FORMULA: 